Method of making carbon nanotube patterned film or carbon nanotube composite using carbon nanotubes surface-modified with polymerizable moieties

Abstract

Disclosed herein are methods of making a negative pattern of carbon nanotubes or a polymerized carbon nanotube composite having an interpenetrating polymer network (IPN) by modifying the surfaces of the carbon nanotubes with polymerizable functional groups such as oxirane and anhydride groups and subjecting the surface-modified carbon nanotubes either to a photolithography process or to a heatcuring process. By virtue of the present invention, desired patterns of carbon nanotubes can be easily made on the surfaces of various substrates, and polymerized carbon nanotube composites improved in hardening properties can be made without additional polymers.

1. A surface-modified carbon nanotube comprising:
 an oxirane group of formula (1) and/or with an anhydride group of formula (2), (3), (4), (5), (6) or (7) directly bonded to the surface thereof: 
 
       
         
           
           
               
               
           
         
         wherein, R is C 1-15 , linear, branched or cyclic alkylene; 
       
       
         
           
           
               
               
           
         
       
     
     
       2. A composition comprising surface-modified carbon nanotubes comprising:
 an oxirane group of formula (1) and/or with an anhydride group of formula (2), (3), (4), (5), (6) or (7) directly bonded to the surface thereof: 
 
       
         
           
           
               
               
           
         
         wherein, R is C 1-15 , linear, branched or cyclic alkylene; 
       
       
         
           
           
               
               
           
         
       
     
     
       3. The composition according to  claim 2 , further comprising:
 at least one coupling agent at 0.1-10 parts by weight based on 100 parts by weight of the surface-modified carbon nanotubes, 
 wherein the at least one coupling agent is one or more selected from the group consisting of aminopropyltriethoxysilane, phenylaminopropyltrimethoxysilane, ureidopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, isocyanatopropyltriethoxysilane, isopropyltriisostearoyltitanate, and acetoalkoxyaluminium diisopropylate. 
 
     
     
       4. The composition according to  claim 2 , further comprising:
 an oxirane group-containing monomer, oligomer or polymer, and/or an anhydride group-containing monomer, oligomer or polymer at 1-95 parts by weight based on 100 parts by weight of the surface-modified carbon nanotubes. 
 
     
     
       5. The composition according to  claim 2 , further comprising:
 at least one polymer binder at 1-30 parts by weight based on 100 parts by weight of the surface-modified carbon nanotubes, 
 wherein the at least one polymer binder is one or more selected from the group consisting of polyester, polycarbonate, polyvinylalcohol, polyvinylbutylal, polyacetal, polyarylate, polyamide, polyamideimide, polyetherimide, polyphenyleneether, polyphenylenesulfide, polyethersulfone, polyetherketone, polyphthalamide, polyethernitrile, polybenzimidazole, polycarbodiimide, polysiloxane, polymethylmethacrylate, polymethacrylamide, nitrile rubber, acryl rubber, polyethylenetetrafluoride, epoxy resin, phenol resin, melamine resin, urea resin, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene, polystyrene, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated polyisoprene, and hydrogenated polybutadiene. 
 
     
     
       6. A composition comprising:
 (a) surface-modified carbon nanotubes including an oxirane group of formula (1) and/or with an anhydride group of formula (2), (3), (4), (5), (6) or (7) directly bonded to the surface thereof; and 
 (b) one or more photoacid or photobase generator, 
 
       
         
           
           
               
               
           
         
       
       wherein, R is C 1-15 , linear, branched or cyclic alkylene; 
       
         
           
           
               
               
           
         
       
     
     
       7. The composition according to  claim 6 , wherein the composition comprises 3-95 wt % of the surface-modified carbon nanotubes and 0.1-15 parts by weight of the photoacid or photobase generator based on 100 parts by weight of the surface-modified carbon nanotubes. 
     
     
       8. The composition according to  claim 6 , further comprising:
 at least one photo intensifier at 0.3-2 parts by weight based on 100 parts by weight of the surface-modified carbon nanotubes, 
 wherein the at least one photo intensifier is one or more selected from the group consisting of 2-ethyl-9,10-dimethoxyanthracene, 9,10-dichloroanthracene, 1-chloro-anthracene, 2-methylanthracene, 9-methylanthracene, 2-t-butylanthracene, anthracene, 1,2-benzanthracene, 1,2,3,4-dibenzanthracene, 1,2,5,6-dibenzanthracene, 1,2,7,8-dibenzanthracene, 9,10-dimethoxydimethylanthracene, 2-ethyl-9,10-dimethoxyanthracene, N-methylphenothiazine, and isopropylthioxanthone. 
 
     
     
       9. The composition according to  claim 6 , further comprising:
 at least one organic solvent selected from the group consisting of DMF, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monoethyl ether, 2-methoxyethanol, methoxypropylacetate, ethyl-3-ethoxy-propionate, and cyclohexanone. 
 
     
     
       10. A composition comprising:
 (a) surface-modified carbon nanotubes including an oxirane group of formula (1) and/or with an anhydride group of formula (2), (3), (4), (5), (6) or (7) directly bonded to the surface thereof; and 
 (b) one or more thermal hardener, 
 
       
         
           
           
               
               
           
         
       
       wherein, R is C 1-15 , linear, branched or cyclic alkylene; 
       
         
           
           
               
               
           
         
       
     
     
       11. The composition according to  claim 10 , wherein the composition comprises 3-95 wt % of the surface-modified carbon nanotubes and 1-35 parts by weight of the thermal hardener based on 100 parts by weight of the surface-modified carbon nanotubes. 
     
     
       12. The composition according to  claim 10  further comprising:
 at least one organic solvent selected from the group consisting of DMF, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monoethyl ether, 2-methoxyethanol, methoxypropylacetate, ethyl-3-ethoxypropionate, and cyclohexanone. 
 
     
     
       13. The composition according to  claim 10 , further comprising:
 at least one coupling agent at 0.1-10 parts by weight based on 100 parts by weight of the surface-modified carbon nanotubes, 
 wherein the at least one coupling agent is one or more selected from the group consisting of aminopropyltriethoxysilane, phenylaminopropyltrimethoxysilane, ureidopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, isocyanatopropyltriethoxysilane, isopropyltriisostearoyltitanate, and acetoalkoxyaluminium diisopropylate. 
 
     
     
       14. The composition according to  claim 10 , further comprising:
 an oxirane group-containing monomer, oligomer or polymer, and/or an anhydride group-containing monomer, oligomer or polymer at 1-95 parts by weight based on 100 parts by weight of the surface-modified carbon nanotubes. 
 
     
     
       15. The composition according to  claim 10 , further comprising:
 at least one polymer binder at 1-30 parts by weight based on 100 parts by weight of the surface-modified carbon nanotubes, 
 wherein the at least one polymer binder is one or more selected from the group consisting of polyester, polycarbonate, polyvinylalcohol, polyvinylbutylal, polyacetal, polyarylate, polyamide, polyamideimide, polyetherimide, polyphenyleneether, polyphenylenesulfide, polyethersulfone, polyetherketone, polyphthalamide, polyethernitrile, polybenzimidazole, polycarbodiimide, polysiloxane, polymethylmethacrylate, polymethacrylamide, nitrile rubber, acryl rubber, polyethylenetetrafluoride, epoxy resin, phenol resin, melamine resin, urea resin, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene-diene copolymer, butyl rubber, polymethylpentene, polystyrene, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated polyisoprene, and hydrogenated polybutadiene.